CROSS REFERENCE TO RELATED APPLICATION
This application is a Continuation-In-Part of Divisional application Ser. No. 11/941,549 filed 16 Nov. 2007, which in turn is a Divisional of U.S. application Ser. No. 10/778,997 filed 12 Feb. 2004, now granted as U.S. Pat. No. 7,316,788.
This invention was made with Government support under Contract DE-AC0676RLO-1830 awarded by the U.S. Department of Energy. The Government has certain rights in the invention.
FIELD OF THE INVENTION
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The present invention relates generally to materials and processes for storing hydrogen, and uses for same. More particularly, the present invention relates to bulk-scaffolded materials, compounds, materials, and combinations that provide storage and release of bulk quantities of hydrogen at lower release temperatures and faster release rates for operation of hydrogen-fueled on-board and off-board devices and applications.
BACKGROUND OF THE INVENTION
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The Department of Energy (DOE) issued a challenge for hydrogen storage related technologies during 2003 to compliment existing programs on Hydrogen Production and Fuel Cell development. Part of the challenge involved proposed project milestones in calendar years 2010 and 2015 for the development of new materials and technologies relating to storing hydrogen for use as vehicle energy sources. Four technologies for storing hydrogen are under investigation in the technical art: (1) storage as simple metal hydrides, e.g., MgH2, (2) storage on carbon materials, including single-walled carbon nanotubes, (3) storage as complex metal hydrides, e.g., NaAlH4, and (4) chemical hydrogen storage, e.g. NHxBHx, where x=1 to 4. The technical developments related to chemical hydrogen storage technology are discussed further hereafter. Baitalow et al. have shown the potential for use of N-B-H compounds including ammonia borane (AB), NH3BH3, as a hydrogen storage material. Jaska et al. report hydrogen formation in AB is likely to occur by an intermolecular dimerization pathway as shown in reaction , although a two-step mechanism shown in reactions  and  is not ruled out:
Each step that forms a new B—N bond also forms hydrogen, as illustrated in reactions  and :
Baitalow et al. further report at temperatures greater than 150° C., additional hydrogen may be released as illustrated in reactions  and :
However, it is well known in the art that release of hydrogen from neat AB occurs at temperatures at which undesirable side reactions occur thereby generating products that contaminate and decrease the purity of the released hydrogen for use as fuel. For example, formation of cyclic borazine, c-(NHBH)3, an inorganic analog of benzene, is one such contaminating product reported by Wideman et al., illustrated in reaction :
Raissi et al. have reviewed data for hydrogen release from the neat solid AB. The reaction of NH3BH3 that yields NH3(BH2—NH2)nBH3+free nH2 releases hydrogen at temperatures near 115° C. in reactions that are comparatively slow and that again have a high potential for forming borazine. At even moderate reaction temperatures (e.g., >150° C.), borazine yields are significant. Borazine is damaging to fuel cells. Thus, its presence means the purity of released hydrogen remains questionable and thus unsuitable for use.
As the current state of the art shows, use of AB materials remains problematic due to: 1) relatively high reaction temperatures required for hydrogen release, 2) slow rates for release of hydrogen, and 3) presence of contaminants like borazine that contaminate the hydrogen released from the source materials that complicate their use as a fuel source.
Accordingly, there remains a need to: 1) decrease temperatures at which hydrogen is released to meet proposed guidelines for bulk hydrogen fuel storage and use; 2) improve rates for hydrogen release; and 3) minimize side reactions that generate undesirable and contaminating products thereby increasing the purity of hydrogen that is available as a fuel.
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OF THE INVENTION
The present invention provides materials, methods and mechanisms for storing and releasing hydrogen in a way that produces greater rate yields at lower temperatures than are found in the prior art while simultaneously preventing undesired side reactions and providing released hydrogen with sufficient purity so as to allow for various hydrogen energy based applications. The materials of the present invention provide greater capacities for storage and release of hydrogen in a pure state and thus have the potential to serve numerous industrial applications wherein high hydrogen storage and usage demands may be met, including, but not limited to, next generation fuel cells and hydrogen sources, applicable to uses in the automobile industry and elsewhere.
In one embodiment the invention is a bulk-scaffolded hydrogen storage and releasing material, made up of a preselected ratio of at least one hydrogen storage and releasing compound combined with a porous support to form a bulk-scaffolded hydrogen storage that releases a bulk quantity of hydrogen at a greater rate, a lower temperature, than the hydrogen storage compound alone. In one embodiment of the invention the hydrogen storage and releasing compound comprises about 30% to about 99% of said material by weight. In another embodiment of the invention the porous support comprises between about 70% to about 1% of said material by weight. This porous support can have pores in a variety of sizes either uniform or random and can also be doped with a metal ion or metal oxide. The hydrogen storage and releasing compound can be any of a variety of suitable materials, however it has been shown that the following materials in particular are beneficial to achieve the desired results and effect: Li, Be, B, C, N, O, F, Na, Mg, Al, Si, P, and combinations thereof. In other applications, the material for storing and releasing hydrogen currently and preferably comprises a member selected from the group of N—B—H compounds, including, but not limited to, ammonia borane (AB) that when deposited onto a support or scaffolding material, the composition exhibits unique and useful properties for storing and releasing hydrogen. Other materials suitable for use as hydrogen storing and releasing compounds or materials include: chemical hydrides, complex hydrides, metal hydrides, polymers, conducting polymers, nitrogen boron compounds, boron nitride, carbon materials, and combinations thereof. Support materials include, but are not limited to, members selected from the group of porous materials, interconnected materials, non-interconnected materials, channeled materials, aerogels, aerogel materials, polymer materials, porous polymer materials, nonporous materials, mesoporous materials, zeolites, zeolite materials, silica, silicon dioxide, mesoporous silica, titanium dioxide, mesoporous titanium dioxide, carbon materials, carbon nanotubes, activated carbon materials, graphite materials, mesoporous carbon materials, and combinations of these materials.
In various embodiments of the invention, the porous materials may be a microporous material, having a pore sizes ranging between 0.4 nm and 2 nm, while in other applications these materials may be a mesoporous material having a pore size ranging between 2 nm to 50 nm while in some other applications the support is a macroporous material having a pore size ranging between 50 nm to 1000 nm. These porosities can vary but is generally preferred to be at least 20% porosity by volume. In addition the types of porous supports can vary however it has been shown that materials such as silica, alumina, and carbon are effective.
The ratio of hydrogen storage and releasing compounds together with the porous support is typically somewhere within the range of from (1:2) to (4:1) by weight, respectively. The bulk scaffolded materials release hydrogen at a temperature at least ten degrees lower than said hydrogen storage and releasing compound alone. This results in materials that can reliably release relatively clean hydrogen at a desired rate of release at temperatures below 95° C., and in some applications even less than about 85° C. In addition to these lower temperatures of release these bulk-scaffolded materials can release stored hydrogen at rates at least twice that of the rate of hydrogen release of the hydrogen storage and releasing compound alone. In some applications this can be as high as one order of magnitude greater than the rate of hydrogen release of the hydrogen storage and releasing compound alone. These advantages can be combined in a variety of structures and materials including hydrogen fuel source, a hydrogen storage material or an accessory to various electrical applications. This provides potential applications for powering a variety of devices ranging from electronic devices, to fuel cells [e.g., solid oxide and proton exchange membrane (PEM) fuel cells], to hydrogen sources that provide power to accessories in the automobile industry, and to hydrogen powered combustion engines. Such compounds can enable a variety of applications in a combined system such as an automobile where hydrogen can be used to power a variety of associated and interactive systems. In other applications, these compounds can provide fuel to power fuel cells that can be expected to provide energy in such devices as laptops and cell phones and may be used to power such accessories as air conditioners, radios, power windows, sun roofs, and global positioning satellite (GPS) devices in automobiles.
The method of preparing the hydrogen storage materials of the instant invention includes the steps: 1) providing a support composed of a high surface area material, and 2) combining the support with at least one compound capable of storing and releasing hydrogen, wherein the compound(s) when deposited on the support releases hydrogen at a greater rate and a lower temperature relative to the neat material. The term “combining” as used herein describes various chemical and physical processes, including, but not limited to impregnating, depositing, layering, coating, physisorbing, chemisorbing, mixing, wetting, polymerizing, chemically bonding, and combinations thereof. The resulting composite material for storing and releasing hydrogen may be adapted for both on-board and off-board applications, including but not limited to, on-board devices, off-board devices, hydrogen generators, fuel sources and components, solid oxide fuel cells and associated components, as well as constituents and/or components in/for engines, including, but not limited to, vehicle engines, combustion engines, automobile engines, and the like.
Materials of the present invention provide greater capacities for storage and release of hydrogen in a pure state, at lower temperatures and/or greater release rates, and thus have the potential to serve numerous industrial applications where high hydrogen usage demands may be met, including, but not limited to, next generation fuel cells [e.g., solid oxide and proton exchange membrane (PEM) fuel cells] and hydrogen sources, applicable to uses in the automobile industry, and elsewhere. For example, fuel cells are expected to provide energy in such devices as laptops and cell phones and may be used to power such accessories as air conditioners, radios, power windows, sun roofs, and global positioning satellite (GPS) devices in automobiles.
The purpose of the foregoing abstract is to enable the United States Patent and Trademark Office and the public generally, especially the scientists, engineers, and practitioners in the art who are not familiar with patent or legal terms or phraseology, to determine quickly from a cursory inspection the nature and essence of the technical disclosure of the application. The abstract is neither intended to define the invention of the application, which is measured by the claims, nor is it intended to be limiting as to the scope of the invention in any way.
Various advantages and novel features of the present invention are described herein and will become further readily apparent to those skilled in this art from the following detailed description. In the preceding and following descriptions I have shown and described only the preferred embodiment of the invention, by way of illustration of the best mode contemplated for carrying out the invention. As will be realized, the invention is capable of modification in various respects without departing from the invention. Accordingly, the drawings and description of the preferred embodiment set forth hereafter are to be regarded as illustrative in nature, and not as restrictive.
BRIEF DESCRIPTION OF THE DRAWINGS
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FIG. 1a is a high resolution transmission electron micrograph (HRTEM) that shows a cross-sectional view of a support comprised of a porous silicate template, i.e., SBA-15.
FIG. 1b is an HRTEM that shows a transverse view of a porous silicate template, i.e., SBA-15.
FIG. 2 shows the unique temperature profile for release of hydrogen from a 1:1 AB:SBA-15 composite compared to neat AB.
FIG. 3 presents mass-spectral data for hydrogen release as a function of DSC thermal decomposition temperature for a 1:1 AB:SBA-15 composite, a 2:1 AB:SBA-15 composite, and a 3:1 AB:SBA-15 composite.
FIG. 4 presents mass-spectral data for release of hydrogen gas from a 1:1 AB:SBA-15 composite as a function of DSC thermal decomposition temperature that shows a low release temperature for hydrogen with an absence of contaminating reaction products.
FIG. 5 compares hydrogen release data from a 1:1 AB:SBA-15 composite material and neat AB.
FIG. 6 presents mass-spectral data for hydrogen release as a function of DSC thermal decomposition temperature for a 1.77:1 AB:MCM-41 composite.
FIG. 7 presents 11B NMR spectra of various AB:MCM-41 composites showing the change in the boron environment as a function of loading.
FIG. 8 compares DSC-TG data for AB:MCM-41 composites at weight ratios of from (1:1) to (3:1) to neat AB.
FIG. 9 compares hydrogen release at 130° C. for AB:MCM-41 composites at weight ratios of from (1:1) to (4:1).
FIG. 10 plots the change in heat (measured by DSC) and release of hydrogen [measured by mass spectrometry (MS)] from the (1:1) AB:SBA-C material as a function of temperature.
The following terms are used herein.
The term “bulk-scaffolded hydrogen storage and releasing material” as used herein means a preselected quantity of at least one hydrogen storage and releasing compound that is combined, mixed, or otherwise associated with a scaffold, support, or template material. Bulk-scaffolded materials of the invention include between from about 30 wt % to about 99 wt % of a hydrogen storage and releasing material and between from about 70 wt % to about 1 wt % of a scaffold, Support, or template material. Bulk-scaffolded materials of the invention are configured to release or deliver a bulk quantity of hydrogen sufficient for operation of a hydrogen-fueled device or application. Bulk-scaffolded materials of the invention are not catalysts, by definition, because hydrogen released or delivered by these materials is consumed and must be regenerated or recharged, but does not exclude addition of a catalyst to the matrix of the hydrogen storage and releasing component. Thus, no limitations are intended. Results described herein demonstrate that bulk-scaffolded materials of the invention alter or affect at least one of the following properties or parameters: the thermodynamics of reaction, temperatures of reaction, kinetics and rates of reactions, including combinations of these properties.
The term “neat” as used herein means a hydrogen storage and releasing material before it is combined with a scaffold or support. Neat materials can include a single hydrogen storage and releasing material or compound (e.g., 100% or pure); more than one hydrogen storage and releasing material (e.g., in a 50:50 combination); more than two hydrogen storage and releasing materials (e.g., in a 50:20:10 combination or the like), as well as other combinations.
The term “bulk” as used herein in reference to bulk-scaffolded materials of the invention means a preselected and suitable quantity of a hydrogen storage and releasing material that is combined with a scaffold or support. The term when used in reference to the quantity of hydrogen released from a bulk-scaffolded hydrogen storage and releasing material means a quantity of hydrogen other than a catalytic quantity sufficient for operation of a hydrogen-fueled device, e.g., a fuel cell or a combustion engine.
The term “catalytic quantity” means a quantity of a catalyst that is less than 10% by weight. By definition, a catalyst is not consumed in a reaction, does not alter the thermodynamics of a reaction, and can only affect the rate of a reaction.
The term “support” as used herein means a high surface area compound or material that is combined with a hydrogen storage material to form a bulk scaffolded hydrogen storage and releasing material.
The term “template” in reference to the materials of the present invention refers to molecules, macromolecules, compounds, and/or material combinations that serve as patterns for the generation or synthesis of other macromolecule(s), compounds, and/or features being deposited, coated, laid down, and/or polymerized.
The term “pore” as used herein means a cavity, depression, or channel present of a scaffold, support, or template material that permits entry of, or that retains, a hydrogen storage and releasing material. The term “pore” encompasses various shapes including, but not limited to, e.g., round and square. A scaffold, support, or template material that includes these pores is said to be “porous”. Pores in these scaffolds, supports, and template materials are also of preselected sizes. Porous materials include, but are not limited to, interconnected porous materials, non-interconnected porous materials, ordered porous materials, non-ordered porous materials, and porous materials that include, e.g., pores, channels, features, and combinations of these elements. Supports of the present invention are preferably made of porous materials that are mesoporous, but are not limited thereto. For example, porous materials may also include microporous and macroporous materials. Porous materials can further include a plurality of pores, features, and/or channels. Materials that include pores, channels, and features as will be selected by those of skill in the art in view of the disclosure are within the scope of the invention, including manufacturing and/or application methods. In particular, those skilled in the art will appreciate that hydrogen storage and releasing materials described herein, as well as related moieties, including, e.g., chemical products and/or intermediates can be applied to various templates, supports, and substrates of a porous or nonporous type to preparation bulk scaffolded hydrogen storage and releasing materials of the invention. Thus, no limitations are intended.
The term “microporous” as used herein means pores with a size in the range from about 0.4 nm to 2 nm.
The term “mesoporous” as used herein means pores with a size in the range from about 2 nm to 50 nm.
The term “macroporous” as used herein means pores with a size in the range from about 50 nm to 10,000 nm.
The term “high surface area” in reference to scaffold, support, or template materials means a surface area of at least about 50 m2/g.
The term “combining” as used herein describes various chemical and physical processes, including, but not limited to impregnating, depositing, layering, coating, physisorbing, chemisorbing, mixing, wetting, polymerizing, chemically bonding, and combinations thereof.
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OF THE INVENTION
Bulk-scaffolded hydrogen storage and releasing materials are described herein that provide bulk quantities of hydrogen for hydrogen-fueled devices and like applications. While the present invention is described herein with reference to the preferred embodiments thereof, it should be understood that the invention is not limited thereto, and various alternatives in form and detail may be made therein without departing from the scope of the invention.
FIG. 1a and FIG. 1b show high resolution transmission electron microscope (HRTEM) images of a support 100 material used in conjunction with the invention in cross-section and transverse views, respectively. Support 100 is a template material comprised of, e.g., mesoporous silica nanoparticles, e.g., Santa Barbara Amorphous type [SBA-15 (SBA)]. Support materials serve as templating substrates whereby bulk hydrogen storage and releasing materials are deposited, impregnated, deposited, chemi-sorbed, physi-sorbed, coated, polymerized, and/or chemically bound at correct weight ratios. The nature of the surfaces (both interior and exterior) of the substrate or support allow contouring, mimicking, and/or mirroring the detail or pore structure of the substrate surface on which the bulk hydrogen storage material is deposited or in chemical communication with. Support 100 can include both porous and non-porous materials of a high surface area, i.e., of at least about 50 m2/g. Porous silica templates have an extremely high surface area and a highly ordered pore structure. Silica (SiO2) is a preferred support material for the template reactions of the present invention by virtue of the pore structure, but is not intended to be limited thereto. Support 100 comprises a plurality of pores or channels. Pores of a support material are preferably of a size in the range from about 0.4 nm to 10,000 nm. Pores of microporous support materials are preferably selected in the range from about 0.4 nm to about 2 nm. Pores of mesoporous support materials are preferably selected in the range from about 2 nm to about 50 nm. Pores of macroporous support materials size are preferably selected in the range from about 50 nm to 10,000 nm. Suitable materials for support 100 can further include porous carbon (e.g., mesoporous carbon), porous TiO2 (e.g., mesoporous titanium dioxide), porous Al2O3 (e.g., mesoporous alumina) and like supports, including supports made of support materials doped or coated with metal ions or metal oxides. Support materials can further include porous silica and porous carbon doped or coated with, e.g., aluminum (Al+3) and/or titanium (Ti+4), or those doped or coated with, e.g., Al2O3 and/or TiO2. Support 100 may be further formulated in a variety of shapes or particle configurations specific to the intended application. For example, support materials may be comprised of, or take the form of, nanoparticles, nanospheres, colloidal particles, and combinations of these material types. Particles of the present invention, including, but not limited to, nanoparticles and colloidal particles, are preferably of a size in the range from about 1 nm to about 10 μm. Support 100 is combined with at least one compound having a high weight or volume ratio density of hydrogen, although more than one compound can be envisioned. Materials for storing and releasing hydrogen preferably include at least one element selected from the group consisting of Li, Be, B, C, N, O, Na, Mg, Al, Si, P, S, or combinations thereof. Exemplary materials with these elements include, but are not limited to, e.g., LiBH4, NaBH4, Mg(BH4)2, AlH3, LiAlH4, Li3N (i.e., LiNH2+LiH), MgH2, LiH, B(OH)3, RSiH3, RSiH2R, including combinations of these compounds. Other elements and exemplary compounds include, but are not limited to, e.g., Ca [e.g., Ca(BH4)2, Ca(NH2BH3)2)]; Ti [e.g., Ti(NH2BH3)4]; and Al[Al(NH2BH3)4]. No limitations are intended by the disclosure of exemplary compounds.
More preferably, materials for storing and releasing hydrogen are selected from the group of NHxBHx compounds where x is in the range from about 1 to 4, ammonia borane (NH3BH3) being representative, but not exclusive. For example, metal hydrides, complex hydrides, other chemical hydrogen storage materials (e.g., ammonia, NH3), and/or mixtures thereof can be envisioned. Combining support 100 and compound(s) having a high weight percentage of hydrogen (i.e., >30 wt %) produces a material exhibiting uncharacteristic properties that include a faster release rate and a lower release temperature for hydrogen relative to neat materials (i.e., material not combined with the support) themselves. Ammonia borane (AB) as a hydrogen storing and releasing material is preferably deposited or fashioned at thicknesses whereby the AB hydrogen storage and releasing material is combined at a 1:1 weight ratio with the support 100 or scaffolding substrate thereby yielding a 1:1 composite material, e.g., 1:1 AB:SBA-15, but is not limited thereto. For example, other weight ratios between the AB hydrogen storing and releasing material and the SBA support 100 are easily accommodated. For example, AB:SBA weight ratios of 1:2, 1:3, and greater, or alternatively AB:SBA weight ratios of 1:1, 2:1, 3:1 and greater may be deployed to maximize hydrogen storage and release. Choices as will be selected by those of ordinary skill in the art are within the scope of the invention.
Porous materials used as the support or template material preferably comprise at least about 20% porosity by volume. The high surface area support material is preferably selected from the group consisting of porous nanoparticles, porous coated nanoparticles, and combinations thereof. Porous coated nanoparticles may be selected from the group consisting of externally coated, internally coated, both externally/internally coated, internally Filled, internally filled/externally coated, and combinations thereof.
Non-porous materials may be used as supports or scaffold materials if they have a sufficiently high surface area. Non-porous materials are preferably selected from the group of non-porous nanoparticles, externally coated non-porous nanoparticles, and combinations thereof. Examples of a non-porous support include, but are not limited to, a composite comprising nanoscale features or channels, e.g., non-porous nanoparticles and/or non-porous spheres. It should be noted that to further enhance the kinetics or thermodynamics for hydrogen release and uptake, catalysts and catalyst like materials may be added to the support(s), hydrogen storage material(s), or the bulk-scaffolded hydrogen storage and releasing materials of the invention. For example, adding a transition metal catalyst and/or a carbon material to the bulk-scaffolded hydrogen storage and releasing material can be used to enhance kinetics or thermodynamics for release of hydrogen from these materials. Catalysts as would be envisioned or deployed by a person of ordinary skill in the art are within the scope of the invention.
Solvents for preparing materials of the present invention include hydrocarbon and organic solvents such as methanol, ethanol, diethyl-ether, tetrahydrofuran, and supercritical fluids of water, ammonia, and carbon dioxide. Preferred solvents provide rapid drying of dissolved hydrogen storage and releasing materials once combined with, or deposited on, the support whereby the hydrogen storage and releasing materials quickly and efficiently bond to the support. No limitations in the selection of applicable solvents is hereby intended by the disclosure of the preferred solvent.